Cutting oil



Patented Apr. 1, 1952 CUTTING OIL Samuel Manilych, Brooklyn, and Lee L. Lambert, Flushing, N. Y., assignors to Socony-Vacuum Oil Company, Incorporated, New York, N. Y., a

corporation of New York No Drawing. Application April 8, 1949, Serial No. 86,383

13 Claims. I

The present invention relates to mineral oil compositions comprising a base oil of petroleum origin and hydroabietyl alcohol and, more par-- ticularly, to mineral oil compositions suitable for use as cutting oils and containing a mixture of hydrogenated abietyl alcohols and rosin hydrocarbons.

Dehydroabietyl alcohol. dihydroabietyl alcohol and tetrahydroabietyl alcohol together with a small proportion of esters of hydrogenated rosin and hydrocarbons are available industrially under the name hydroabietyl alcohol." The mixture available to industry under the name hydroabietyl alcohol is composed of 13-15 per cent 0! a non-alcohol fraction and the balance of a mixture or hydrogenated abietyl alcohols in which about 15 per cent is dehydroabietyl alcohol, about 40 per cent is dihydroabietyl alcohol and the balance, about 45 per cent, is tetrahydroabietyl alcohol. The non-alcohol portion of hydroabietyl alcohol varies with the saponiflcaticn number but will average about 3-8 per cent oi the total mixture in the form or esters which can be considered as methyl esters of hydrogenated rosin and the remainder, 7-12 per cent of the total mixture, is similar to the hydrocarbon iractions occurring in hydrogenated rosin.

The physical properties and composition of the material available under the name hydroabietyl alcohol and comprising the aforesaid mixture of alcohols, esters and hydrocarbons are as follows:

Hydroxyl value 5.0-5.1 per cent Hydroabletyl alcohol 85-87 per cent Sponiflcatlon number (diethyl- U. S. Rosin Standard Z1 Softening point (drop method)- 33 C. Specific gravity at 20/20 0---. 111074.008

(Cl. 252-48A) 2 Refractive index at 20 C 1.528 Flash point (C. 0. C.) 185-195 C. Flame point (C. O. C.) 217-220 C.

5 It has long been the practice to enhance the value of mineral oil for use as a cutting lubricant by the addition of various materials such as esters to the lubricating fraction 01 mineral oil. Other cutting oils having as bases suliurized mineral oil, chlorinated mineral oil or sulfurized and chlorinated mineral oil or a mixture of sulfurized mineral oil and chlorinated mineral oil in combination with a lubricating fraction of mineral oil of suitable viscosity have also been used in conjunction with additives such as esters, and stain inhilitors. The ester type of additive, particularly those made by esterifying an hydroxy aliphatic dicarboxylic acid with a monohydric aliphatic alcohol having more than 10 carbon atoms in the molecule and those made by esteritying one hydroxyl group of a low molecular weight dihydric alcohol with an aliphatic acid having more than 10 carbon atoms in the molecule and then esterifying the other hydroxyl group of the dihydric alcohol with an hydroxyl aliphatic dicarboxylic acid has been iound particularly useful as an oiliness additive. It now has been discovered that vastly improved results can be produced by employing the aforedescribed hydroabietyl alcohol as an oiliness agent in the formulation of cutting oils.

Before describing the novel cutting oil compositions it is believed well to identity the alcohols present in hydroabietyl alcohol and indicate the probable structure thereof. The hydroabietyl alcohol industrially available is composed 0! an alcohol traction and a non-alcohol fraction. As noted herelnbefcre about 3-8 per cent of the total mixture is esters which may be considered methyl esters of hydrogenated rosin and about 7-12 per cent at the total mixture is similar to the hydrocarbon fractions occurring in hydrogenated resin. The balance is about 14-23 percent dehydroabietyl alcohol, about 36-39 per cent dihydroabietyl alcohol and about 38-50 per cent 3 tetrahydroabietyl alcohol. It will be observed that the structures of both dehydroabietyl alcohol and dihydroabietyl alcohol are structures of unsaturated alcohols and that all three alcohols have the hydroxyl group attached to the nucleus through a methylene group. The hydroabietyl alcohols may be considered as related to phenanthrene. This relationship is recognized readily by consideration of the following struc- 4 to that of the standard and a relative efliciency is calculated on a percentage basis. For example:

Torque with standard reference oil 19.3 Torque with test oil 19.8 Relative efliciency of test oil tural formulae: 10 It might be added that the cuttin oils are CH: CH: C0011 1 1 AW I 12, 14

cn, CH on. -c 11 7 11 CH: CHi Phenanthrenc Retene Abletlc acid (l-methyl-T-isopropyl) pbenanthrene CH: CHIOH UH: CHaOH CH; CHZOH H cn, cn; H 0H,

(3-H C\-H .11

CHI CH: CH; Dehydroabietyl alcohol Dlhydroabietyi alcohol Tetrahydroahietyl alcohol The effectiveness of "hydroabietyl alcohol," i. e., the commercially available mixture of the three hydroabietyl alchols, hydrocarbons and methyl esters of hydrogenated rosin was compared with that of two ester type additives in a moderately sulfurized oil containing 0.9 per cent active sulfur. The blends tested comprised 99 parts by weight sulfurized pale oil having a viscosity of 150 S. U. seconds 100 F. and containing about 0.9 per cent active sulfur and l per cent of the ester type additive, 99 weight per cent sul furized pale oil of 150 seconds SUV containing about 0.9 per cent active sulfur and 1 weight per cent of commercially available hydroabietyl alcohol, and 95 weight per cent of the sulfurized oil containing 0.9 per cent active sulfur and weight per cent commercially available hydroabietyl alcohol.

The blends were subjected to three tests, viz.: tapping efficiency, Oster threading efliciency and drill life tests. These tests are performed as described hereinafter.

TAPPING TEST In the measurement of tapping efiiciency of an oil, a series of holes are very accurately drilled in a test metal, namely SAE 1020 hot rolled steel. These holes are subsequently tapped with a series of taps, in a drill press equipped with a table, which is free to rotate about the center, being mounted on ball bearings. A torque arm is attached to this floating table and this arm in turn actuates a spring scale so that the actual torque during tapping with the oil being evaluated is measured directly. The same taps used in evaluating the test 011 are employed in tapping with a standard reference oil, which has arbitrarily been assigned an emciency of 100 per cent. The average torque for the test oil is compared applied to the taps by means of a circulation system.

OSTER THREADING TEST The threading test is conducted on an Oster pipe threading machine by threading four, 4" pieces of SAE 1020 steel pipe. During these operations the power consumption is graphically recorded on a wattmeter as each oil is evaluated. At the end of the test the average net power required to thread the four nipples is calculated. In this manner. the power measurement is made on a standard reference oil and then the operation is repeated on the unknown oil. The threading efficiency of the unknown oil is then calculated by arbitrarily assigning an efliciency of per cent to the reference oil and calculating the comparative efficiency of the unknown on a power requirement basis. The mathematics used are similar to those illustrated in the tapping test.

DRILL LIFE TEST The drill life test is determined by using ten drill uniformly ground to specified angles, three of which are placed in the chucks of a triple spindle head of the drill press at the start of the test. Holes are then drilled through flats of SAE 3140 steel until drill failure occurs. This is evidenced by excessive noise, tool burning and deterioration of the cutting edges. The failed drill is replaced with a newly ground one and the test is continued until all ten drills fail. The drill life with any oil is the average of the number of holes obtained per drill. During the test a continuous flow of cutting oil is supplied to each drill.

The results of the foregoing tests are tabulated in Table I.

1 Compound oil having mineral oil base and containing 0.9 per cent active sulfur.

I Compound oil having mineral oil base and containing at least 0.8 per cent non-corrosive sulfur and at least 0.75 per cent chlorine.

Additive HOll is an ester of an hydroxy aliphatic dicarboxylic acid in which one carboxyl group is csteril'ied by commercial hydroabietyl alcohol and the other carboxyl group is esterifled by a high molecular-weight aliphatic alcohol.

Additive M is an ester of a low molecular weight dihydrlc alcohol estarifled with a high molecular weight all stic monocarboxylic acid and then esterifled with a low molecu ar weight aliphatic dicarboxylic acid. I

Additive D00 is an ester of an hydroxy aliphatic dicarboxyiic acid in which both carhoxyl groups have been esteriiled by a high molecular weight aliphatic alcohol.

It will be noted that the most readily discerned difference is in the number of holes which can be drilled before a drill must be retired. The base oil containing 0.9% active sulfur permitted the drilling of 51 holes before the drill was retired. One ester type additive (DGO) when added to the base oil increased the drill life about 16 per cent; a second ester type additive (MGO) increased drill life about 26 per cent; the third ester type additive (HOH) increased drill life about 55 per cent. However, 1 per cent commercial hydroabietyl alcohol increased drill life 90 per cent or almost doubled the life of the drill.

Satisfactory results can be obtained when employing other base oils as for example, mineral oil of lubricating grade admixed with a moderately sulfurized mineral oil containing about 0.9 per cent active sulfur and a chlorinated parafilne base containing about 42 per cent chlorine. The commercially available hydroabietyl alcohol can be mixed with the aforementioned components and other additives such as stain inhibitors, antioxidants, etc. to provide a composite oil having a composition coming within the ranges set forth hereinafter:

Broad Preferred Formula Formula Formula A:

Moderate] sulfurlzed Mineral oil contalning a ut 0.9% active sulfur; per

cent 0-09 30-00 Chlorinated base containing about 42% chlorine; per cent 0-15 (Y-T Mineral oil 50-500"@100 F. SUV; per

can 0-99 0-62 Commercial Hydr per cent 0. 1-10 0. 25-2 Formula 13:

Sulfurisod-chlorlnated fatty oil containing about sulfur and about 5% Cl, per cent 0. 25-15 0. 5-4. 0 Mineral oil, 50 500"@l00 F. SUV;

per cent 78-09 05-99 Stain Inhibitor; per cent 0-2 0.1-0.5 Commercial Hydroabietyl Alcohol;

per cent 0.1-5 0. 25-0. 5

In view of the foregoing it is manifest that improved results can be obtained in gear lubricants, cutting oils and the like by incorporating commercial hydroabietyl alcohol in the compound oil as an oillness additive. Those skilled in the art will understand that other additives such as stain inhibitors, antioxidants and the like can also be incorporated in the usual amounts.

While the Tapping, Threading and Drill Life" tests indicate that esters having both carboxyl groups of a hydroxy aliphatic polycarboxyilc acid esterified with radicals from hydroabietyl alcohol mixture are all more effective than similar esters of aliphatic alcohols there is an advantage to the use of either mixed esters or mixtures of esters. This advantage results from the viscosity of the various esters. As is manifest after a consideration of the following tabulation of viscosities of various esters, di-hydroabietyl malate, for example, is far more viscous than the mixed esters. The high viscosity of the dl-hydroabietyl esters makes it desirable to reduce the viscosity without sacrificing a disproportionate amount of the effectiveness of the hydroabietyl esters. As will be appreciated by study of the following tabulation this can be done by using mixed esters.

Consequently, for ease of manufacture and incorporation in oil blends it is preferred to employ a mixed ester of an alpha-hydroxy polycarboxylic acid derived from 50 mole per cent of hydroabietyl alcohol and 50 mole per cent oleyl alcohol, 1. e., from the reaction of 1 mole of hydroabietyl alcohol, 1 mole of oleyl alcohol and 1 mole of polycarboxylic acid. Fluidity of the product can be obtained by employing mixed esters of alphahydroxy polycarboxylic aliphatic acids in which from 50 mole per cent to 99 mole per cent hydroabietyl radical and from i to 50 mole per cent of an alkyl radical are present in the carbalkoxy groups. The alkyl groups are those derived from monohydric aliphatic saturated or unsaturated alcohols having from one through 18 carbon atoms and includes oleyl alcohol.

Mixed esters containing '75 mole per cent hydroahietyl, 25 mole per cent oleyl ester may be made in any of the following or other suitable procedures.

A. Hydroabietyl alcohol (about 1.5 moles) oleyl alcohol (about 0.5 mole) and alpha-hydroxy aliphatic polycarboxyiic acid (about 1.0 mole) are reacted as described hereinbefore.

B. About mole parts of di-hydroabietyl ester of an alpha-hydroxy aliphatic poiycarboxylic acid and about 25 mole parts of di-oleyl ester of an alpha-hydroxy aliphatic polycarbcxyllc acid are heated together until ester exchange has occurred.

C. Equal parts of mole per cent hydroabietyl-l5 mole per cent oleyl ester of an alphahydroxy aliphatic polycarboxylic acid and of 65 mole per cent hydroabietyl-35 mole per cent oleyl ester of an alpha-hydroxy aliphatic polycarboxylic acid are heated together until ester exchange has occurred. Thus, for example, the esters may be the malates.

It is to be noted that while the neutral esters are satisfactory for use in cutting oils it is preferred to use esters which are a mixture of neutral and partial esters for anti-rust agents. Therefore it is preferred to use esters having a neutralization number of zero to 30 in cutting oils but esters having a minimum neutralization number oi. 10 in anti-rust oils, such as turbine oil:-

In the copending application for United States Letters Patent Serial No. 86,382, filed April 8, 1949, now Patent No. 2,564,634, patented August 14, 1951, in the names of Leslie C. Beard and Ralph V. White, there is a disclosure of the improved results accruing irom the use of an ester of a. hydroxy aliphatic polycarboxylic acid in which at least one carboxyl group of said acid is esterifled by hydroabietyl alcohol in turbine oils, cutting oils and the like. It has been discovered that the improved results obtained by incorporating an ester of the class defined hereinbefore in mineral oil compositions can be still further improved by incorporating hydroabietyl alcohol in addition to the aforesaid ester. This will become apparent from the data presented in Table II for cutting oil compositions.

' Compound oil having mineral oil base and containing 0.9 per cent activc an] r.

Additive HOH is an ester of a hydroxy aliphatic dlcarbox lic acid in which one carbcxyl group is esterified by commercial by abietyl alcohol and the other carboxyl group is esterilled by a high molecular wei ht aliphatic alcohol.

Additive Hill) is an ester oi a hydroxy all )hatlc dlcarbox llc acid in which boih oarboxy] groups are esterlfic by commercla hydroabietyl alcohol.

Additive "E0 is an ester oi an hydroxy aliphatic dicarbox 'llc acid in which one carboxyl group is csterllled by commercial by ro ahietyl alcohol and the other cnrboxyl group is esterliled by a monohydrie aliphatic alcohol having eight carbon atoms in the molecule.

Additive liai is commercial hydroabietyl alcohol.

It will be noted that when about 25% of the hydroabietyl ester additive is replaced by hydroabietyl alcohol per se the properties of the blend are superior to those of the blend of base oil and ester. Thus, for example, the drill life, when the base oil is used without ester or hydroabietyl alcohol, is only 51 holes. When 1 weight per cent of additive HOH is incorporated in the base oil the drill life is increased 55%, i. e., from 51 to '79 holes. When 0.75% HOH and 0.25% hydroabietyl alcohol are incorporated in the base oil the drill life is increased 71%. Thus, it is evident that improved results can be obtained not only when hydroabietyl alcohol is the sole additive for this purpose but also when the hydroabietyl alcohol is only 25% of the total additive of this class present in the oil. Therefore, it is within the scope oi the present invention to use 0.1 to 5% or hydroabietyl alcohol or a mixture of hydroabietyl alcohol and an ester of an hydroxy aliphatic polycarboxylic acid in which at least one carboxyl group is esterifled by hydroabietyl alcohol, said ester being present in an amount not greater than 4 times the concentration of the hydroabietyl alcohol and the minimum concentration of hydroabietyl alcohol per se being 0.20 weight per cent.

As those skilled in the art will understand other additives such as stain inhibitors, anti-oxidants and the like can also be incorporated in the usual 8 amounts in addition to the additives specifically defined hereinbeiore.

We claim:

1. A compound oil consisting essentially of a mineral oil base of lubricating grade containing about 0.9 per cent active sulfur and commercial hydroabietyl alcohol in amount of 0.1 to about 10% effective to increase drill life.

2. A compound oil consisting essentially oi a mineral oil base of lubricating grade. containing at least 0.8 per cent non-corrosive sulfur, at least 0.75 per cent chlorine and commercial hydroabietyl alcohol in amount or 0.1 to about 10% effective to increase drill life.

3. A compound oil consisting essentially of Per cent Mineral oil containing about 0.9% active sulfur 30-00 Chlorinated base containing about 42% chlorine 0-? Mineral 011, 50-500 seconds S. U. V.

100 F 042 Commercial hydroabietyl alcohol 0.25-2

4. .A compound oil consisting essentially of Per cent Suliurized-chlcrlnated fatty oil containing about 5% sultur and about 5% chlorine 0.25-15 Mineral 011, 50-500 seconds 8. U. V.

100 F 78-09 Stain inhibitor 0-2 Commercial hydroabietyl alcohol 0.1-5

5. A compound oil consisting essentially of Per cent Sulfurized-chlorinated fatty oil containingabout 5% sultur and about 5% chlorine 0.5-4.0 Mineral 011, 50-500 seconds 8. U. V.

100 F. -99 Stain inhibitor 0.1-0.5

Commercial hydroabietyl alcohol 025-05 6. A compound oil consisting essentially of a major proportion of a lubricating fraction of mineral oil containing about 0.0 per cent active sulfur and an amount of 0.1 to about 10% silictive to increase drill life of a mixture 0! commercial hydroabietyl alcohol and esters oi malic acid, said mixture oi. hydroabietyl alcohol and esters consisting essentially of at least 0.2 weight per cent hydroabietyl alcohol and the balance an ester product of mallc acid in which about 50-100 mol per cent or the radicals attached to the carbonyl carbon atoms through oxygen in radicals oi hydroabietyl alcohol and the balance is a radical oi' monohydric aliphatic alcohol having 11-20 carbon atoms, the concentration or said esters in said mixture being not greater than (our times the concentration of said commercial hydroabietyl alcohol and said esters having a minimum neutralization number 01' 10.

7. A compound oil consisting essentially of a major proportion of a lubricating fraction of mineral oil containing about 0.9 per cent active sulfur and an amount 01' 0.1 to about 10% eflective to increase drill life of a mixture of commercial hydroabietyl alcohol and esters of malic acid, said mixture consisting essentially oi at least 0.2 weight per cent commercial hydroabietyl alcohol and the balance an ester product 0! mile acid in which about 50-100 mol per cent of the radicals attached to the carbonyl carbon atoms through oxygen is radicals of commercial hydroabietyl alcohol and the balance is a radical oi monohydric aliphatic alcohol having 8-20 carbon atoms, said ester being present in said mixture of commercial hydroabietyl alcohol and ester in a concentration not greater than four times the concentration of said commercial hydroabietyl alcohol, said ester having a neutralization number of zero to 30 and the concentration of said commercial hydroabietyl alcohol in said compound oil being at least 0.20 weight per cent.

8. A compound oil consisting essentially of a mixture of hydroabietyl alcohol and an ester 0.1 chlorinated base containing about 42% chlorine 045%, and the balance not to exceed 99% 0! at least one oleaginous vehicle selected from the group consisting of mineral oil containing about 0.9% active sulfur and mineral oil of 50-500 seconds S. U. V. 100 F., said mixture of hydroabietyl alcohol and ester consisting essentially of at least 0.2 weight per cent hydroabietyl alcohol and the balance an ester product of malic acid in which about 50-100 mol per cent of the radicals attached to the carbonyl carbon atoms through oxygen is radicals of hydroabletyl alcohol and the balance is a radical of monohydric aliphatic alcohol having 820 carbon atoms. said ester being in a concentration not greater than four times the concentration of said hydroabietyl alcohol, and said ester having a neutralization number of zero to 30.

9. A compound oil as described an set forth in claim 8 wherein the mixture of hydroabietyl alcohol and an ester consists essentially of a mixture of commercial hydroabietyl alcohol and esters containing '75 mole per cent of an ester of malic acid and an alcohol derived from commercial hydroabietyl alcohol and 25 mole per cent of an ester of malic acid and oleyi alcohol.

10. A compound oil as described and set forth in claim 8 wherein the ester consists essentially of 75 mole per cent of an ester of malic acid and an alcohol derived from commercial hydroabietyl alcohol and 25 mole per cent of an ester of said malic acid and oleyl alcohol.

11. A compound oil as described and set forth 10 in claim 8 wherein the ester consists essentially of mixed esters of malic acid in which to 99 mole per cent of the carbalkoxy groups is derived from commercial hydroabietyl alcohol and 1 to 50 mole per cent of the carbalkoxy groups is an alkyl group having 1 to 18 carbon atoms.

12. A compound oil as described and set forth in claim 8 wherein the ester consists essentially of mixed esters of malic acid in which 50-99 mole percent of the carbalkoxy group is derived from commercial hydroabietyl alcohol and, 1 to 50 mile per cent of the carbalkoxy groups is derived from a monhydric aliphatic alcohol having 1 through 18 carbon atoms.

13. A compound oil consisting essentially of commercial hydroabietyl alcohol 0.1 to 10%, chlorinated base containing about 42% chlorine 045% and the balance not to exceed 99% of at least one oleaginous vehicle selected from the group consisting of mineral oil of 50-500 seconds 8. U. V. 100 F. and mineral oil containing about 0.9% active sulfur.

SAMUEL MANILYCH. LEE L. LAMBERT.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,021,100 Henke Nov. 12. 1935 2,094,127 Lazier Sept, 29, 1937 2,142,989 Barrett Jan. 10, 1939 2,268,608 McNulty Jan. 6, 1942 2,274,617 Remy Feb. 24, 1942 2,384,595 Blair Sept. 11, 1945 2,430,058 Klaber Nov. 4, 1947 2,443,578 Fuller June 15, 1948 2,564,638 Beard et ai Aug. 14, 1951 OTHER REFERENCES "New Products and Materials" in Chemical Engineering. Jan. 1948, p. 173. 

1. A COMPOUND OIL CONSISTING ESSENTIALLY OF A MINERAL OIL BASE OF LUBRICATING GRADE CONTAINING ABOUT 0.9 PER CENT ACTIVE SULFUR AND COMMERCIAL HYDROABIETYL ALCOHOL IN AMOUNT OF 0.1 TO ABOUT 10% EFFECTIVE TO INCREASE DRILL LIFE. 